Confinement effects for ionic carriers in SrTiO3 ultrathin films: first-principles calculations of oxygen vacancies: First-principles calculations of oxygen vacancies

One-dimensional confinement effects are modelled within the hybrid HF-DFT LCAO approach considering neutral and single-charged oxygen vacancies in SrTiO₃ ultrathin films. The calculations reveal that confinement effects are surprisingly short-range in this partly covalent perovskite; already for film thickness of 2-3 nm (and we believe, similar size nanoparticles) only the surface-plane defect properties differ from those in the bulk. This includes a pronounced decrease of the defect formation energy (by ∼1 eV), a much deeper defect band level and a noticeable change in the electronic density redistribution at the near-surface vacancy site with respect to that in the bulk. The results also show that the size effect pertains to the interactions between the oxygen vacancy and two neighboring titanium atoms and orientation (parallel or perpendicular to the surface) of the Ti-V_O-Ti complex. In particular, we predict considerable oxygen vacancy segregation towards the surface.